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Autoxidation
Autoxidation (sometimes auto-oxidation) refers to oxidations brought about by reactions with oxygen at normal temperatures, without the intervention of flame or electric spark. The term is usually used to describe the gradual degradation of organic compounds in air at ambient temperatures. Many common phenomena can be attributed to autoxidation, such as food going rancid, the ' drying' of varnishes and paints, and the perishing of rubber. It is also an important concept in both industrial chemistry and biology. Autoxidation is therefore a fairly broad term and can encompass examples of photooxygenation and catalytic oxidation. The common mechanism is a free radical chain reaction, where the addition of oxygen gives rise to hydroperoxides and their associated peroxy radicals (ROO•). Typically, an induction period is seen at the start where there is little activity; this is followed by a gradually accelerating take-up of oxygen, giving an autocatalytic reaction which can on ...
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Hydroperoxide
Hydroperoxides or peroxols are Chemical compound, compounds of the form ROOH, where R stands for any group, typically Organic compound, organic, which contain the hydroperoxy functional group (). Hydroperoxide also refers to the hydroperoxide anion () and its Salt (chemistry), salts, and the neutral hydroperoxyl, hydroperoxyl radical (•OOH) consist of an unbond hydroperoxy group. When R is organic, the compounds are called organic hydroperoxides. Such compounds are a subset of organic peroxides, which have the formula ROOR. Organic hydroperoxides can either intentionally or unintentionally initiate explosive polymerisation in materials with saturated bond, saturated chemical bonds. Properties The bond length in peroxides is about 1.45 Ångström, Å, and the angles (R = Hydrogen, H, Carbon, C) are about 110° (water-like). Characteristically, the dihedral angles are about 120°. The bond is relatively weak, with a bond dissociation energy of , less than half the strength ...
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Polyunsaturated Fats
In biochemistry and nutrition, a polyunsaturated fat is a fat that contains a polyunsaturated fatty acid (abbreviated PUFA), which is a subclass of fatty acid characterized by a backbone with two or more carbon–carbon double bonds. Some polyunsaturated fatty acids are essential fatty acid, essentials. Polyunsaturated fatty acids are precursors to and are derived from polyunsaturated Fat, fats, which include drying oils. Nomenclature The position of the carbon-carbon double bonds in carboxylic acid chains in fats is designated by Greek alphabet, Greek letters. The carbon atom closest to the carboxyl group is the ''alpha'' carbon, the next carbon is the ''beta'' carbon and Locant#Greek_letter_locants, so on. In fatty acids the carbon atom of the methyl group at the end of the hydrocarbon chain is called the ''omega'' carbon because ''omega'' is the last letter of the Greek alphabet. Omega-3 fatty acids have a double bond three carbons away from the methyl carbon, whereas omega- ...
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Allyl
In organic chemistry, an allyl group is a substituent with the structural formula . It consists of a methylene bridge () attached to a vinyl group (). The name is derived from the scientific name for garlic, . In 1844, Theodor Wertheim isolated an allyl derivative from garlic oil and named it "". The term allyl applies to many compounds related to , some of which are of practical or of everyday importance, for example, allyl chloride. Allylation is any chemical reaction that adds an allyl group to a Substrate (chemistry), substrate. Nomenclature A site adjacent to the unsaturated carbon atom is called the allylic position or allylic site. A group attached at this site is sometimes described as allylic. Thus, "has an allylic hydroxyl group". Allylic Carbon–hydrogen bond, C−H bonds are about 15% weaker than the C−H bonds in ordinary Orbital hybridisation, sp3 carbon centers and are thus more reactive. Benzylic and allylic are related in terms of structure, bond strength ...
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Cumene Process
The cumene process (cumene-phenol process, Hock process) is an industrial process for synthesizing phenol and acetone from benzene and propylene. The term stems from cumene (isopropyl benzene), the intermediate material during the process. It was invented by R. Ūdris and P. Sergeyev in 1942 (USSR), and independently by Heinrich Hock in 1944. This process converts two relatively cheap starting materials, benzene and propylene, into two more valuable ones, phenol and acetone. Other reactants required are oxygen from air and small amounts of a radical initiator. Most of the worldwide production of phenol and acetone is now based on this method. In 2022, nearly 10.8 million tonnes of phenol was produced by the cumene process. In order for this process to be economical, there must also be demand for the acetone by-product as well as the phenol. Steps of the process Cumene is formed in the gas-phase Friedel–Crafts alkylation of benzene by propene. Benzene and propene are compr ...
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Rancidification
Rancidification is the process of complete or incomplete autoxidation or hydrolysis of fats and oils when exposed to air, light, moisture, or bacterial action, producing short-chain aldehydes, ketones and free fatty acids. When these processes occur in food, undesirable odors and flavors can result. In processed meats, these flavors are collectively known as warmed-over flavor. In certain cases, however, the flavors can be desirable (as in aged cheeses). Rancidification can also detract from the nutritional value of food, as some vitamins are sensitive to oxidation. Similar to rancidification, oxidative degradation also occurs in other hydrocarbons, such as lubricating oils, fuels, and mechanical cutting fluids. Pathways Five pathways for rancidification are recognized: Hydrolytic Hydrolytic rancidity refers to the odor that develops when triglycerides are hydrolyzed and free fatty acids are released. This reaction of lipid with water may require a catalyst (such as a ...
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Linseed Oil
Linseed oil, also known as flaxseed oil or flax oil (in its edible form), is a colorless to yellowish oil obtained from the dried, ripened seeds of the flax plant (''Linum usitatissimum''). The oil is obtained by pressing, sometimes followed by solvent extraction. Owing to its polymer-forming properties, linseed oil is often blended with combinations of other oils, resins or solvents as an impregnator, drying oil finish or varnish in wood finishing, as a pigment binder in oil paints, as a plasticizer and hardener in putty, and in the manufacture of linoleum. Linseed oil use has declined over the past several decades with increased availability of synthetic alkyd resins—which function similarly but resist yellowing. Structure and composition : 450px, Representative triglyceride found in a linseed oil, a triester ( , and Linseed oil is a triglyceride, like other fats. Linseed oil is distinctive for its unusually large amount of α-linolenic acid, which oxidises in ...
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Catalytic Oxidation
Catalytic oxidation are processes that rely on catalysts to introduce oxygen into organic and inorganic compounds. Many applications, including the focus of this article, involve oxidation by oxygen. Such processes are conducted on a large scale for the remediation of pollutants, production of valuable chemicals, and the production of energy. Oxidations of organic compounds Carboxylic acids, ketones, epoxides, and alcohols are often obtained by partial oxidation of alkanes and alkenes with dioxygen. These intermediates are essential to the production of consumer goods. Partial oxidation is challenging because the most favored reaction between oxygen and hydrocarbons is combustion. Oxidations of inorganic compounds Sulfuric acid is produced from sulfur trioxide which is obtained by oxidation of sulfur dioxide. Food-grade phosphates are generated via oxidation of white phosphorus. Carbon monoxide in automobile exhaust is converted to carbon dioxide in catalytic converters. Exam ...
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Autocatalysis
In chemistry, a chemical reaction is said to be autocatalytic if one of the reaction products is also a catalyst for the same reaction. Many forms of autocatalysis are recognized.Steinfeld J.I., Francisco J.S. and Hase W.L. ''Chemical Kinetics and Dynamics'' (2nd ed., Prentice-Hall 1999) pp. 151–2 A ''set'' of chemical reactions can be said to be "collectively autocatalytic" if a number of those reactions produce, as reaction products, catalysts for enough of the other reactions that the entire set of chemical reactions is self-sustaining given an input of energy and food molecules (see autocatalytic set). Examples Acid-catalyzed hydrolysis of esters produces carboxylic acids that also catalyze the same reaction. Indeed, the observation of an accelerating hydrolysis of gamma valerolactone to gamma-hydroxyvaleric acid led to the introduction of the concept of autocatalysis in 1890. The oxidation of hydrocarbons by air or oxygen is the basis of autoxidation. Like many radic ...
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Antioxidants
Antioxidants are Chemical compound, compounds that inhibit Redox, oxidation, a chemical reaction that can produce Radical (chemistry), free radicals. Autoxidation leads to degradation of organic compounds, including living matter. Antioxidants are frequently added to industrial products, such as polymers, fuels, and lubricants, to extend their usable lifetimes. Foods are also treated with antioxidants to prevent Food spoilage, spoilage, in particular the rancidification of Vegetable oil, oils and fats. In Cell (biology), cells, antioxidants such as glutathione, mycothiol, or bacillithiol, and enzyme systems like superoxide dismutase, inhibit damage from oxidative stress. Known diet (nutrition), dietary antioxidants are vitamins vitamin A, A, vitamin C, C, and vitamin E, E, but the term has also been applied to various compounds that exhibit antioxidant properties in vitro, having little evidence for antioxidant properties in vivo. Dietary supplements marketed as antioxidants hav ...
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Radical Disproportionation
Radical (from Latin: ', root) may refer to: Politics and ideology Politics *Classical radicalism, the Radical Movement that began in late 18th century Britain and spread to continental Europe and Latin America in the 19th century *Radical politics, the political intent of fundamental societal change * Radical Party (other), several political parties *Radicals (UK), a British and Irish grouping in the early to mid-19th century *Radicalization *Politicians from the Radical Civic Union Ideologies * Radical chic, a term coined by Tom Wolfe to describe the pretentious adoption of radical causes * Radical feminism, a perspective within feminism that focuses on patriarchy * Radical Islam, or Islamic extremism * Radical Christianity * Radical veganism, a radical interpretation of veganism, usually combined with anarchism * Radical Reformation, an Anabaptist movement concurrent with the Protestant Reformation Science and mathematics Science * Radical (chemistry), an atom, molecule ...
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Sigmoid Function
A sigmoid function is any mathematical function whose graph of a function, graph has a characteristic S-shaped or sigmoid curve. A common example of a sigmoid function is the logistic function, which is defined by the formula :\sigma(x) = \frac = \frac = 1 - \sigma(-x). Other sigmoid functions are given in the #Examples, Examples section. In some fields, most notably in the context of artificial neural networks, the term "sigmoid function" is used as a synonym for "logistic function". Special cases of the sigmoid function include the Gompertz curve (used in modeling systems that saturate at large values of ''x'') and the ogee curve (used in the spillway of some dams). Sigmoid functions have domain of all real numbers, with return (response) value commonly monotonically increasing but could be decreasing. Sigmoid functions most often show a return value (''y'' axis) in the range 0 to 1. Another commonly used range is from −1 to 1. A wide variety of sigmoid functions ...
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Polymer Auto-oxidation
A polymer () is a substance or material that consists of very large molecules, or macromolecules, that are constituted by many repeating subunits derived from one or more species of monomers. Due to their broad spectrum of properties, both synthetic and natural polymers play essential and ubiquitous roles in everyday life. Polymers range from familiar synthetic plastics such as polystyrene to natural biopolymers such as DNA and proteins that are fundamental to biological structure and function. Polymers, both natural and synthetic, are created via polymerization of many small molecules, known as monomers. Their consequently large molecular mass, relative to small molecule compounds, produces unique physical properties including toughness, high elasticity, viscoelasticity, and a tendency to form amorphous and semicrystalline structures rather than crystals. Polymers are studied in the fields of polymer science (which includes polymer chemistry and polymer physics), biophy ...
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